EP0023645B1 - Procédé de préparation de 1,4-diamino-2,3-dicyanoanthraquinones - Google Patents
Procédé de préparation de 1,4-diamino-2,3-dicyanoanthraquinones Download PDFInfo
- Publication number
- EP0023645B1 EP0023645B1 EP80104227A EP80104227A EP0023645B1 EP 0023645 B1 EP0023645 B1 EP 0023645B1 EP 80104227 A EP80104227 A EP 80104227A EP 80104227 A EP80104227 A EP 80104227A EP 0023645 B1 EP0023645 B1 EP 0023645B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- anthraquinone
- acid
- diamino
- sodium
- cyanide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 0 *c(c(N)c1C(c2ccccc22)=O)cc(N*)c1C2=O Chemical compound *c(c(N)c1C(c2ccccc22)=O)cc(N*)c1C2=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/28—Dyes with amino groups substituted by hydrocarbon radicals substituted by alkyl, aralkyl or cyclo alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/22—Dyes with unsubstituted amino groups
Definitions
- the invention relates to a process for the preparation of compounds of the formula in which R is hydrogen or an optionally substituted alkyl or cycloalkyl radical, by reacting corresponding 1,4-diamino-anthraquinone-2 (3) sulfonic acids or their salts with compounds giving off cyanide ions.
- this object is achieved by carrying out the reaction of the ⁇ -sulfonic acids with compounds giving off cyanide ions in formamide or N-methylformamide - preferably in the presence of an oxidizing agent and, if appropriate, in the presence of acid-binding agents.
- formamide is preferred.
- the amount of the solvents to be used according to the invention can vary within a substantial range and essentially depends on the solubility of the reactants. In any case, an easily stirrable system should be formed in which the starting materials are preferably completely dissolved.
- ⁇ -sulfonic acids and their salts are known or are easily accessible by methods known per se.
- Suitable ⁇ -sulfonic acids are 1,4-diamino-anthraquinone-2-sulfonic acid, 1,4-diamino-anthraquinone-2,3-disulfonic acid or their derivatives substituted on the amino group in the 4-position by the radical R.
- Suitable radicals R are: C 1 -C 6 -alkyl, C 1 -C 4 -alkoxy-C 2 -C 5 -alkyl, which can additionally be substituted in the alkoxy group by a hydroxyl group, and cyclohexyl, which is one to can be substituted three times by C 1 -C 3 alkyl radicals.
- R is preferably H or C 1 -C 6 alkyl.
- 1,4-Diamino-anthraquinone-2-sulfonic acid which e.g. particularly environmentally friendly and cost-saving from 1-amino-anthraquinone (mercury-free) by sulfonation, bromination and bromine / amino exchange.
- Suitable oxidizing agents are both inorganic oxidizing agents, such as air, oxygen, nitrites, nitrates, manganese dioxide, sodium chlorite, potassium bromate, ammonium persulfate and potassium persulfate, hydrogen peroxide and its addition compounds, such as sodium percarbonate, sodium perborate and sodium peryrophosphate, as well as organic oxidizing agents, for example peracetic acid, the addition compound of Urea and hydrogen peroxide, nitrobenzene, m-nitrobenzoic acid and its salts and m-nitrobenzenesulfonic acid and its salts.
- inorganic oxidizing agents such as air, oxygen, nitrites, nitrates, manganese dioxide, sodium chlorite, potassium bromate, ammonium persulfate and potassium persulfate
- hydrogen peroxide and its addition compounds such as sodium percarbonate, sodium perborate and sodium peryrophosphate
- organic oxidizing agents for example peracetic
- nitrobenzene m-nitrobenzenesulfonic acid and its salts
- oxygen advantageously in the form of atmospheric oxygen, if appropriate in the presence of heavy metal catalysts, such as ammonium molybdate, ammonium vanadate, or copper compounds, for example copper acetate.
- reaction temperatures can also be varied over a wide range, i.e. fluctuate between 40 and 200 ° C.
- the temperature range used for this synthesis principle namely between 60 and 120 ° C.
- Suitable acid-binding agents are in particular: alkali metal and alkaline earth metal salts of weak acids, such as, for example, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium acetate, potassium acetate, magnesium carbonate and calcium carbonate, and also ammonium carbonate and hydrogen carbonate.
- the amount to be used is mainly determined by the form in which the 1,4-diamino-anthraquinone sulfonic acid is used. If one starts from the free acid, or if free hydrocyanic acid is used as the compound giving off cyanide ions, it is expedient to add at least the equivalent amount of an acid-binding agent. An excess of acid-binding agent does not adversely affect the reaction.
- Suitable compounds which give off cyanide ions are, in particular, alkali metal and alkaline earth metal cyanides, such as sodium, potassium or magnesium cyanide, and furthermore ammonium cyanide, zinc cyanide, copper (I) cyanide, complex copper and zinc cyanides, hydrocyanic acid, cyanohydrins of aldehydes and ketones and the like.
- alkali metal and alkaline earth metal cyanides such as sodium, potassium or magnesium cyanide
- ammonium cyanide zinc cyanide
- copper (I) cyanide copper (I) cyanide
- complex copper and zinc cyanides hydrocyanic acid, cyanohydrins of aldehydes and ketones and the like.
- Sodium cyanide and potassium cyanide are preferred.
- the amount of the compound giving off cyanide ions is to be measured in such a way that for every 1 mol of 1,4-diamino-anthraquinone-2-sulfonic acid or -2,3-disulfonic acid or its salts, at least 2 mol, advantageously 2.5 to 10 mol be used.
- the reaction is complete when the thin layer chromatogram shows the complete conversion of the starting material. This is generally the case after 2-20 hours and depends on the ⁇ -sulfonic acid to be reacted. If the preferred 1,4-diamino-anthraquinone-2-sulfonic acid is used, the reaction is generally complete after 4 hours.
- the solvent can be recovered from the filtrate by simple distillation, which not only saves the process but also avoids wastewater problems.
- the reaction products are immediately obtained in high purity (less than 3% “mononitrile”), which is of great importance for their use as dyes or starting products for the production of valuable dyes (cf. US Pat. Nos. 2628963 and 3203751), since larger contents on «mononitrile» shift the brilliant greenish blue hue to less desirable reddish shades.
- Another advantage of the new production process for these products is that the use of formamide or N-methylformamide as the solvent allows such a reduction in the amount of solvent that the space-time yield compared to the known processes with water as a solvent to about can be increased tenfold.
- the present invention further provides new 1,4-diamino-2,3-dicyanoanthraquinones of the formula (I) in which R represents an optionally substituted cycloalkyl radical, preferably a cyclohexyl radical optionally substituted by 1-3 methyl groups.
- a mixture of 202.8 g of 78.4% 1,4-diamino-anthraquinone-2-sulfonic acid (saline), 41 g of dry sodium acetate, 112.5 g of dry 3-nitrobenzenesulfonic acid sodium, 73.5 g of sodium cyanide and 1200 ccm Formamide is heated to 80-85 ° C. with stirring until after approx. 3.5-4 hours no more starting material can be detected by thin layer chromatography (TLC).
- TLC thin layer chromatography
- the reaction mixture is suctioned off while still warm, the filter cake is washed cold once with 100 cc of formamide and then washed with hot water until it is colorless.
- the reaction can be used with the same success: 84 g sodium hydrogen carbonate, 53 g sodium carbonate, 5 g calcium carbonate, 69 g potassium carbonate, 49 g potassium acetate or 20 g magnesium oxide.
- a mixture of 189.1 g of 84.1% 1,4-diamino-anthraquinone-2-sulfonic acid, 56.3 g of dry sodium 3-nitrobenzenesulfonate, 73.5 g of sodium cyanide and 1200 cc of formamide is brought to 90 ° C. with stirring heated until after 4 hours no more starting material can be detected by TLC.
- the reaction mixture is suctioned off while warm and the filter cake is washed and dried as in Example 1.
- oxidizing agents can also be used with similar success instead of nitrobenzene: 83.5 g of 3-nitrobenzene carboxylic acid sodium, 35 g of sodium nitrite, 43 g of sodium nitrate. Similar results are also obtained if the oxidizing agent used is: manganese dioxide, sodium chlorite, potassium bromate, ammonium persulfate, potassium persulfate, hydrogen peroxide, sodium percarbonate, sodium perborate, sodium perpyrophosphate, peracetic acid or the addition compound consisting of urea and hydrogen peroxide.
- a mixture of 31.8 g of 93.9% 1,4-diamino-anthraquinone-2-sulfonic acid, 240 cc of formamide, 14.7 g of sodium cyanide, 8.2 g of dry sodium acetate and 0.68 g of ammonium vanadate is passed through 6.4 l / hour of air is heated to 80 ° C until the starting material is completely converted (approx. 2.5 hours).
- reaction mixture is worked up as described in the preceding examples and 24.0 g of a dark blue, crystalline product are obtained which, according to analysis, contains 90.9% 1,4-diamino-2,3-dicyano-anthraquinone and 0, Contains 9% 1,4-diamino-2-cyano-anthraquinone. This corresponds to a pure yield of 80.6% dinitrile.
- a correspondingly weaker oxygen stream can be passed through the mixture or, instead of ammonium vanadate, 0.68 g of ammonium molybdate or 1.0 g of copper acetate can be used as a catalyst.
- a mixture of 211 g of 1,4-diamino-anthraquinone-2,3-disulfonic acid sodium, 73.5 g of sodium cyanide, 82 g of dry sodium acetate and 1200 cc of formamide is reduced to 50 until the disulfonic acid has reacted completely (approx. 3 hours) ° C heated.
- the product which has crystallized out is filtered off while still warm, washed with hot water until it is colorless and dried at 60.degree. Yield: 127 g of a dark blue, crystalline product which, according to analysis, contains 95.2% 1,4-diamino-2,3-dicyano-anthraquinone and no mononitrile. This corresponds to a pure yield of 87.9% dinitrile.
- a mixture of 2 g dry sodium carbonate, 75 cc formamide and 2.3 g glacial acetic acid is stirred and mixed with 6.25 g ammonium hydrogen carbonate, 12.7 g dry 3-nitrobenzenesulfonic acid sodium, 8.25 g sodium cyanide and 10 g 1-amino-4 -cyctohexytamino-anthraquinone-2-sulfonic acid sodium added.
- the mixture is heated to 80.degree. C., 7.5 g of glacial acetic acid are added dropwise in about 1 hour and the mixture is then kept at 80-85.degree. C. with stirring until the starting material has reacted completely (about 5 to 6 hours).
- the precipitated dye is filtered off after cooling, washed with hot water to a colorless drain and dried at 60 ° C. Yield: 8.4 g of dark blue crystals, corresponding to 95.8% of theory
- the mass spectrum and the thin layer chromatogram show, it is mainly 1-amino-4-cyclohexylamino-2,3-dicyano-anthraquinone with a molecular weight of 370.
- Nitrogen content calculated 15.12%, found 14.9 / 15, 0%.
- Example 7 7.8 g of dark blue crystals are obtained from 10 g of 1-amino-4-isopropylamino-anthraquinone-2-sulfonic acid sodium (made from isopropylamine and 1-amino-4-bromo-anthraquinone-2-sulfonic acid). corresponding to 90.2% of theory Nitrogen content calculated 16.96%, found 17.1 / 17.2%. As the mass spectrum and thin-layer chromatogram show, it is the mononitrile-free 1-amino-4-isopropylamino-2,3-dicyano-anthraquinone.
- a mixture of 17.7 g of 1-amino-4-methylamino-anthraquinone-2-sulfonic acid sodium, 4.1 g dry sodium acetate, 11.25 g dry 3-nitrobenzenesulfonic acid sodium, 7.35 g sodium cyanide and 120 cc formamide is added Stirring heated to 80-85 ° C until after about 5 hours no more starting material can be detected by thin layer chromatography.
- the reaction mixture is diluted with 120 cc of water, suction filtered at 50 ° C., the filter cake is washed with hot water until it is colorless and dried at 60 ° C.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (7)
où
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19792931981 DE2931981A1 (de) | 1979-08-07 | 1979-08-07 | Verfahren zur herstellung von 1,4-diamino-2,3-dicyano-anthrachinonen |
DE2931981 | 1979-08-07 | ||
DE3003657 | 1980-02-01 | ||
DE19803003657 DE3003657A1 (de) | 1980-02-01 | 1980-02-01 | Verfahren zur herstellung von 1,4-diamino-2,3-dicyano-anthrachinonen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0023645A1 EP0023645A1 (fr) | 1981-02-11 |
EP0023645B1 true EP0023645B1 (fr) | 1982-07-28 |
Family
ID=25780416
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80104227A Expired EP0023645B1 (fr) | 1979-08-07 | 1980-07-18 | Procédé de préparation de 1,4-diamino-2,3-dicyanoanthraquinones |
Country Status (3)
Country | Link |
---|---|
US (1) | US4294769A (fr) |
EP (1) | EP0023645B1 (fr) |
DE (1) | DE3060705D1 (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0034257A2 (fr) * | 1980-02-01 | 1981-08-26 | Bayer Ag | Procédé pour la préparation de 1,4-diamino-2,3 dicyano anthraquinone |
EP0051783A1 (fr) * | 1980-11-08 | 1982-05-19 | Bayer Ag | Procédé de préparation de l'acide 1,4-diamino-anthraquinone-2-sulfonique |
EP0079862A2 (fr) * | 1981-11-18 | 1983-05-25 | Ciba-Geigy Ag | Composés 1,4-diamino anthraquinoniques |
EP0105762A2 (fr) * | 1982-10-04 | 1984-04-18 | Sumitomo Chemical Company, Limited | Procédé pour la préparation de composés anthraquinoniques |
EP0179740A1 (fr) * | 1984-10-26 | 1986-04-30 | Ciba-Geigy Ag | Procédé pour la préparation de la 1,4-diamino-2,3-dicyanoanthraquinone |
EP0275519A2 (fr) * | 1986-12-31 | 1988-07-27 | BASF Aktiengesellschaft | Procédé pour la préparation de 1,4-diamino-2,3-dicyanoanthraquinone |
EP0460496A1 (fr) * | 1990-06-07 | 1991-12-11 | BASF Aktiengesellschaft | Colorants tétra-amino-anthraquinone |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6130550A (ja) * | 1984-07-19 | 1986-02-12 | Sumitomo Chem Co Ltd | 1−アミノ−2−フエノキシ−4−ヒドロキシアントラキノン類の製造方法 |
JPH0721114B2 (ja) * | 1985-12-10 | 1995-03-08 | 住友化学工業株式会社 | アントラキノン化合物の製造方法 |
US4738800A (en) * | 1986-03-26 | 1988-04-19 | Ciba-Geigy Corporation | Process for the preparation of 1,4-diamino-2,3-dicyanoanthraquinones |
CN102993049A (zh) * | 2012-09-07 | 2013-03-27 | 四川省赛南德科技有限公司 | 一种环境友好的制备1,4-二氨基-2,3-二氰基蒽醌的方法 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE536998C (de) * | 1930-03-02 | 1931-10-29 | Ig Farbenindustrie Ag | Verfahren zur Darstellung von Aminoanthrachinonnitrilen |
BE592155A (fr) * | 1959-06-25 | |||
DE1906834U (de) | 1964-09-05 | 1964-12-17 | Glanzstoff Ag | Tufted-teppich. |
CH491876A (de) * | 1968-02-20 | 1970-06-15 | Ciba Geigy | Verfahren zur Herstellung von Derivaten des 1-Aminoanthrachinons |
DE2524748C3 (de) * | 1975-06-04 | 1980-06-04 | Basf Ag, 6700 Ludwigshafen | Verfahren zur Herstellung von 1 ^-Diaminoanthrachinon^-dinitril |
-
1980
- 1980-07-18 DE DE8080104227T patent/DE3060705D1/de not_active Expired
- 1980-07-18 EP EP80104227A patent/EP0023645B1/fr not_active Expired
- 1980-07-24 US US06/171,870 patent/US4294769A/en not_active Expired - Lifetime
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0034257A2 (fr) * | 1980-02-01 | 1981-08-26 | Bayer Ag | Procédé pour la préparation de 1,4-diamino-2,3 dicyano anthraquinone |
EP0034257A3 (en) * | 1980-02-01 | 1981-09-30 | Bayer Ag | Process for the preparation of 1,4-diamino-2,3-dicyano-anthraquinone |
EP0051783A1 (fr) * | 1980-11-08 | 1982-05-19 | Bayer Ag | Procédé de préparation de l'acide 1,4-diamino-anthraquinone-2-sulfonique |
US4521341A (en) * | 1980-11-08 | 1985-06-04 | Bayer Aktiengesellschaft | Process for the preparation of 1,4-diamino-anthraquinone-2-sulphonic acid |
EP0079862A2 (fr) * | 1981-11-18 | 1983-05-25 | Ciba-Geigy Ag | Composés 1,4-diamino anthraquinoniques |
EP0079862A3 (en) * | 1981-11-18 | 1983-10-05 | Ciba-Geigy Ag | 1,4-diamino-anthraquinone compounds |
EP0105762A3 (en) * | 1982-10-04 | 1985-05-15 | Sumitomo Chemical Company, Limited | Process for producing anthraquinone compounds |
EP0105762A2 (fr) * | 1982-10-04 | 1984-04-18 | Sumitomo Chemical Company, Limited | Procédé pour la préparation de composés anthraquinoniques |
EP0179740A1 (fr) * | 1984-10-26 | 1986-04-30 | Ciba-Geigy Ag | Procédé pour la préparation de la 1,4-diamino-2,3-dicyanoanthraquinone |
US4661292A (en) * | 1984-10-26 | 1987-04-28 | Ciba-Geigy Corporation | Process for the preparation of 1,4-diamino-2,3-dicyanoanthraquinone |
EP0275519A2 (fr) * | 1986-12-31 | 1988-07-27 | BASF Aktiengesellschaft | Procédé pour la préparation de 1,4-diamino-2,3-dicyanoanthraquinone |
EP0275519A3 (en) * | 1986-12-31 | 1988-08-17 | Basf Aktiengesellschaft | Process for the preparation of 1,4-diamino-dicyanoanthraquinone |
EP0460496A1 (fr) * | 1990-06-07 | 1991-12-11 | BASF Aktiengesellschaft | Colorants tétra-amino-anthraquinone |
Also Published As
Publication number | Publication date |
---|---|
US4294769A (en) | 1981-10-13 |
DE3060705D1 (en) | 1982-09-16 |
EP0023645A1 (fr) | 1981-02-11 |
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